Hafen-on-the-rhtne



Patented July 7, 1925a UNITE-D, STATES PATENT OFFICE.

PAUL NAXVIASKY WALTER KRANNICH. OF LUDWIGSHAFEN-ON-THE-RHINE,

GERMANY. ASSIGNORS TO BADISCHE ANILIN- .& SODA-FABRIK. F LUDWIGS- HAFEN-ONTHE-RHINE. GERMANY. A CORPORATTON OF GERMANY.

VAT COLORING MATTERS rnonucan BY ,HALOGENA'I'ING 1v-nmYnRmrara-ANTHRA- eumom: AZIN. a v

No Drawing.

ing is a specification.

The invention relates to new-rat coloring matters which excel by valuable tinctori-al properties. As is known, .N-dihydro 1.2.1.2-anthraquinone azin, or iudanthrene while extremely fast to light and other influences. is not so fast to chlorin. Halogen derivatives of said dyestufi have an -improved or even very good fastness to chlorin, but in general, the faster they are to chlorin themore they display a new disadvantage in being sensitive to hard calcareous water in dyeing as the dyeings are con-' siderably weakened thereby. We have now found a new class of halogen derivatives of y N dihydro 1.2.1.2' anthraquinone azin which contains chlorin as well, as hromin and which are both fast to chlorin and practically insensitive to calcareous water.

40 These new vat coloring matters can be obtained bychlorinating and brominating, in this or the inverse succession, N-dihydro- 1.2.1.2-anthraquinone azin. In. case the dyestuff is produced by first 'brominating 5 and then chlorinating the original dyestuff,

the operations are carried out with the latter dissolved in concentrated sulfuric acid, while the inverse operations viz first chlori-nating and then lirominating may be carried out 111 any usual manner, though it is of particular advantage to use a sulfuric acid solution for I the step of brominating and to effect chlori- Application filed October 23, 1923.. Serial No. 670,244.

- nating in a dry condition or also in concen trated sulfuric acid solution. Halogen transporters maybe used in all instances.

The following examples serve to further illustrate the invention and the manner of.

carrying it into effect, but the invention is not limited to these examples; The parts are by weight.

, Example 1.

L4 partsof indanthrene blue RS (N-dihydie-1.2.1'r2-anthraquinone azin) are dissolved in 500 parts of sulfuric acid of 66 degrees Baum, a solution of 1.5 parts of sodium nitrite in 10 parts of sulfuric acid of 66 degrees Baum is then added and a current of chlorin slowly passed through for several hours, at aI-temperature of 60 degrees centigrade. .Then after adding a liti tle more sodium nitrite, dissolved in concentrated sulfuric acid, 16 parts of bromin are gradually introduced and the mixture is kept at 60 degrees centigrade for 10 additional hours. Themixture is then poured into water, the precipitate filtered off, washed until neutral and made into a paste.

Example 2.

A dry mixture of partsof in rlanthrenc blueRS, 15 parts of anhydrous sodium acetate and 5 parts. of ferric chlorid are agitated with 40 parts of chlorin at a temperature of 70 degrees centigrade until all of the chlorin has been consumed, wh'ch requires about 6 or '7 hours. The pr not is" dissolved '11 ten times its weight of sulfuric acid monohydrate and 43 parts of bromin are slowly added, whereupon the solution is degrees Baumg :After adding a solution of 6 parts of sodium'nitrite in 40 parts of sulfuric acid of the" same strength, 16 parts of bromine are allowed to run in slowly, the

solution is then gradually heated to 60 degrees centigrade and kept at this temperature for a few hours. An additional small quantity of sodium nitrite, dissolved in concentrated sulfuric acid, is then addedand a slow current of chlorin passed through thesolution,- while at the same temperature for 6 or 7. hours. The mixture is then worked 'up as described'in the foregoing examples. We'claimz' 1 1. As anew article of manufacture,halogenated N.- dihydro 1.2.1.2' anthraquinone v azin which contains b oth combined chlorin and bfQlllill and which is a blue vat coloring 15 matter, fast to chlorin and practically insensitive to calcareous water in dyeing from the vat.

-' 2.-The process of manufacturing halogenatedvat coloring matters which consists 20 in first chlorinating N-dihydro-l2. 1'.2' an set our hands. r "PAUL 'NAWIASKY.

; WALTER KBANNICH. 

